Alkylenesulfonamides and method of preparing same



United States Patent'Ofiice 3,300,529 Patented Jan. 24, 1967 This is a continuation-in-part application of our copending United States application Serial No. 25,529, filed on April 29, 1960, now abandoned.

The present invention relates to N-alkyl-substituted ethylenesulfonamides and derivatives thereof. More particularly, the instant discovery concerns a novel process for preparing N-alkyl-substituted ethylenesulfonamides wherein a fi-haloethanesulfonyl halide is reacted with an aliphatic primary or secondary amine at a relatively low temperature to produce the corresponding N-alkyl-substituted ethylenesulfonamide.

l-Ieretofore, the compounds which are the object of the present invention have been prepared by a twostep and necessarily cumbersome process as taught by C. S. Rondestvedt, Ir., J. Am. Chem. Soc. 76, 1926 (1954). This process involves the following:

One of the main disadvantages of the Rondestvedt process is that intermediate compound II is highly l-achrymatory and and is violently unstable at room temperature in the presence of certain tertiary bases, e.g., pyridine, which conceivably might be used in the preparation of the intermediate. Compound II, furthermore, must be carefully distilled to avoid decomposition.

Perhaps because compound II is recovered only by a sensitive distillation process, because it is unstable at room temperature, and because of other like difficulties, Rondestvedt reports yields of only 34 percent by weight, based on the e-chloroethanesulfonyl chloride reactant.

According to the present discovery it has been found that the N-alkyl-substituted ethylenesulfonamides, i.e., N,N-dialkyl ethylenesulfonamides and N-alkyl ethylenesulfonamides, may readily be produced in superior yields and in a one-step process not hindered by the necessity for isolating lachrymatory and unstable intermediates. Pursuant to the instant invention a fi-haloethanesulfonyl halide is brought into reactive contact with at least about an equivalent of an aliphatic primary or secondary amine at a temperature in the range of 40 C. to --80 C. and in the presence of a hydrohalide acceptor, such as triethylamine, and the corresponding N-alkyl-substituted ethylenesulfonamide recovered.

If desired, the reaction may be made to take place in the presence of an inert organic solvent, such as chloroform, toluene, or the like.

According to a particular embodiment of the present invention an excess of the reactant aliphatic primary or secondary amine may be used as the hydrohalide acceptor. This will be better understood hereinafter.

Typical primary and secondary amines contemplated herein are diethylamine, ethylamine, dipropylamine, propylamine, dioctylamine, octylarnine, decylamine, didodecylamine, isopropylamine, diisopropylamine, laurylamine, dilaurylamine, methyllaurylamine, Z-ethylhexylamine, stearylamine, distearylamine, octadecylamine, dioctadecylamine, allylamine, diallylamine, morpholine,

piperidine, pyrrolidine, benzylamine, and the like. While these are only typical it is understood that monoaliphatic amines having from 1 to about 20 carbon atoms and di-aliphatic amines having 2 to about 20 carbon atoms are contemplated herein, as well as other cyclic diamines. -As indicated hereinabove, temperatures in the range of 40 C. to C. are suitable; however, preferred temperatures are in the range of 0 C; to about -70 C.

Other inert organic solvents within the purview of the instant discovery are trichloroethylene, perchloroethylene, dichloroethane, benzene, xylene, dioxane, tetrahydro furan, and similar halogenated aliphatic hydrocarbons, aromatic hydrocarbons, and ether solvents which under the conditions of the reaction do not react with the reactants and their products. p

The reactions contemplated herein admit of superatmospheric and sub-atmospheric pressures, as well as atmospheric pressures. In addition, the reactants may be brought together in any desired sequence and reaction may be made to take place in a batch, continuous or semi-continuous manner.

It has been found, pursuant to the instant discovery, that the N-alkyl-substituted ethylenesulfonamides prepared as shown'above may be reacted with at least about a molar equivalent of a hydrohalide to prepare the corresponding 2-halo-N-alkyl-substituted ethanesulfonamide. The following reaction is typical:

The reaction conditions parallel those given hereinabove relative to the preparation of the N-alkyl-substituted ethylenesulfonamide, with the exception that temperatures as high as 60 C. or somewhat higher may be employed. Room temperature (20 C.-25C.) is preferred, however.

These Z-halo-N-alkyl-subsituted ethanesulfonamide derivatives may, in turn, be reacted as disclosed in Belgian Patent 568,089, of May 28, 1958, and French Patent 1,196,415, of November 24, 1959, to prepare useful sulfamoylethyl phosphorodithioate insecticides. 1

Other typical hydrohalide acceptors contemplated herein for preparing N-alkyl-substituted ethylenesulfonamides are pyridine, 2,6-lutidine, collidine, trimethylarnine, tripropylamine, and the like. The hydrohalide acceptor is generally present in the ratio of at least about 2 moles of acceptor per mole of 2-haloethanesulfonyl halide. If desired more than 2 moles, say, up to about 5 moles or more may be employed. This is true also, of. course, if excess primary or secondary amine is used as the hydrohalide acceptor; in such a case, generally at least about 3 moles of the amine per mole of haloethanesulfonyl halide is employed.

The following examples best illustrate the present invention:

EXAMPLE I N-isopropyl ethylenesulfonamide A mixture of 29.5 grams (0.5 mole) of isopropylamine and 101 grams (1.0 mole) of triethylamine is added with stirring over a 15-minute period to a solution of 81.5 grams (0.5 mole) of 2-chloroethanesulfonyl chloride in 1 liter of ether kept at 70 C. with a Dry Ice-actone bath. Stirring is continued for 15 minutes at 70 C. following the addition, then'for an hour while allowing the reaction mixture towarm gradually to 10 C. The triethylamine hydrochloride is filtered off and the filtrate concentrated to milliliters and washed with 15 milliliters of water. Drying over anhydrous sodium sulfate and stripping leaves 39.2 grams (52.5 percent by weight) of an orange liquid which is distilled under vacuum in 3 an atmosphere of nitrogen to give 28.7 grams of a light yellow oil, boiling point 94 C.97 C./0.6 millimeter mercury pressure. Redistillation gives the analytical sample, boiling point 95 C.96.5 C./0.55 millimeter mercury pressure, 11 1.4612, as an almost colorless liquid.

4 EXAMPLE XVIlI 2-br0m0-N,N-dierhyl ethanesulfonamide Hydrogen bromide gas is passed at a moderate rate through an ice-cooled solution of 10 grams (0.065 mole) a freshly distilled N,N-diethyl ethy-lenesulfonarnide (C. EXAMPLE II Rondestvedt, Jr., J. Am. Chem. Soc., 76, 1928 1954 In N,N-dietlzyl etlzylenesulfonamide 100 milliiliiteis of anhydrcus edthelr1 fordathalf hguriz The reaction as is stoppere an -a owe o s an a room A solution of 22.4 grams (0. 3 mole) of dietlylamililie temperature for 7 hours Evaporation of the gather, f l I 31 grams mole) of tnethylamme In d lowed by recrystallization of the residual solid from benof ether added Over a 40 i i zene, with the aid of activated charcoal, gives 12.5 grams stirring grams 1 mole) of 2'c Oroet anesu I (84 percent by weight) of fine white needles, melting Fony c-hlo-rlde m mllhhters 3 ether The temperaiure point 56.5 C.5 8 C. Two additional recrystalliz'ations 1S man-named at 9 5 by means of an Icefrom ether yield analytically pure material melting at 58 methanol bath. Stirring is continued for another hour at 0 C this temperature after which the precipitated triethyl- EXAMPLE XIX amine hydrochloride is filtered off and the filtrate concentrated under vacuum to give 24.grams of a brown 2-br0m0-N-is0pr0pyl ethanesulfonamide hquld' gg gs gi gs jg i 20 Hydrogen bromide gas is passed through a solution of gratrns 0 Pro lir eo P 1 4602 N-isopropyl ethylenesulfonamide (14.9 grams, Olmole) me ers mercury press in 200 milliliters of reagent-grade ether, with stirring for E AM E III 1.5 hours. The rate of addition is adjusted to keep the C The solution t] l l 1 temperature between C. and 34 i 1y 8 hy enesu fonamlde 25 gradually becomes orange. After an additional one-hour s The Procedure 15 the Same as that of Example H W1th standing at room temperature in a closed flask, the ether the exception that grams mole) 9 dieihylamine solution is Washed with 20 milliliters of water. The Water s used a fOhOWlng the removal of the 'lrlethylamine Y- layer is extracted with three SO-milliliter portions of ether, drOehlOride, filtrate is washed With 5 Percent y followed by 3 50-milliliter portions of chloroform. It is h acid. d dried Over magnesium Sulfate There 30 necessary to add water in order to obtain separation of 3S Obtained grams of Product, boiling Point 0 the phases during the chloroform extraction. The com- C1055 millimeter mercury Pressure bined ether solution and extracts and the chloroform extracts are dried over anhydrous sodium sulfate and the EXAMPLE IV solvents removed under vacuum. There are obtained 19.2 N,N-diethyl ethylenesulfonamide 35 grams (84 percent by weight) of tan crystals, melting t ives The procedure of Example III is followed with the C 94 C .Recrystalhzmon from e her g a th t th t6 mm is maintained at light pink crystals which are freed of adsorbed hydrogen Z a a i I t bath bromide by slurrying' in 20 percent potassium bicarbonate 5 d g if 0 8 g g g 6 solution, filtering, washing several times with Water, and l y 0 pro 01 3 3 4Q drying in a vacuum desiccator over calcium chloride; yield mnhmeter mercury pressure 18 grams 14.2 grams (62 percent by weight) of light pink crystals,

EXAMPLES V XVH melting point 945 C.96 C. i

' i By following the procedure and conditions given in Example II. above, is rep a in e y essential r Examples XVIII or XIX, the Z-halo-N-alkyl-substituted spect except that the changes and substitutions appearing ethanesulfonamides corresponding to the products of E in the following table are made: amples III to XVII, above, are similarly produced.

TABLE I Reactants Example Solvent Hydrolialide Teinpera- Product Acceptor turc, C. 2lialoethancsulfonyl halide Amine 2-blrtlimogtl anesultonyl Ethylaminc Chloroiorm Pyridine -40 N-ethyl ethyleiiesulfoiianiidc.

C1 Oll e. 2-ehloroetlianesuli'onyl Dioctylaminc... Toluene 2,6-lutidiiie N,N-oety1ethylenesulchloride. loiiarnide. I do Dccylalnine Perchloroethylene. Collidine -4 N-decyl ethylcnosulfonamitlc. JIII do Laurylaininc Ether 2,6-lutidinc N-dodaecyletliylencsulfon- IX 2-bromoethancsull'ony1 Dilanrylzunine.. Dichloroethanefifl Triethylainine -70 Nf l l diilodccyl ethylciicsulclilor' c. ionamide. K 2-chloroethanesull'onyl Methyllauryla- Dioxanc Pyridine H -70 N-metliyl-N-dodecyl ethylchloride. mine. enesulionamidc.

Oetadecylaminc Tctrahydr0luran Excess octadec- 10 N-octadecyl ethylenesulylamine. fonamide. Z-ethylhcxylarnine- Benzene I. Excess 2-ethylhex- 0 N-zetliylhexyl ethylenesulylarnine.* lonamide. Piperidine Tricthylainine 70 N-etliylenesulfonyl pipcridinc. Morpholine -I Excessgnorpho- 35 Nicthylenesulionylmorpho- 1 e. Allylamiiie Etlicr Triet hylainincnn -70 N-iiilylethylenesuli'onaniide. Diallylainine do do 15 N,N-diallyl'etliylciiesulfonainidc. Benzylainine d0 (lo .I -70 N genzyl ethylenesulionani- *By excess is meant two molar equivalents (in addition to the amine reactant) per mole of 2-haloethaiiesullonyl halide reactant.

The following examples illustrate the conversion puruant to the present invention of N-alkyl-substituted ethyl- :ne sulfonamides, prepared as in Examples I-XVII, .b'ove, to their corresponding 2-ha'lo-N-alkyl-substituted ithanesulfonainides.

the scope of the invention, except insofar as they appear in the appended claims.

We claim:

1. A method which comprises reacting a [i-halo-ethanesulfonyl halide with one molar equivalent of a member selected from the group consisting of alkyl amine having from 1 to 20 carbon atoms, di-alkyl amine in which each alkyl has from 2 to 20 carbon atoms, alkenyl amine having from 3 to 20 carbon atoms, di-alkenyl amine in which each alkenyl has from 3 to 20 carbon atoms, and benzylamine at a temperature in the range of 40 C. to -80 C. and in the presence of an amine hydroha-lide acceptor, and recovering the resulting corresponding ethylenesulfonamide.

2. The process of claim 1 wherein the reaction is made to take place in the presence of an inert organic solvent.

3. The process of claim 1 wherein the temperature is in the range of C. to -70 C.

4. The process of claim 1 wherein the hydrohalide acceptor is the amine reactant present in excess of at least two molar equivalents.

5. The process of claim 1 wherein the halide reactant is fl-chloroethanesulfonyl chloride, the amine is diethylamine, the temperature is 0 C. to --70 C. and the hydroha-lide acceptor is triethylamine.

6. The process of claim 1 wherein the halide is B-chloroethanesulfonyl chloride.

7. The process of claim 1 wherein the halide is fi-bromoethanesulfonyl chloride.

8. The process of claim 1 wherein the amine is diethylamine.

9. The process of claim 1 wherein the amine is isopropylamine.

10. The process of claim 1 wherein the amine is dioctylamine.

11. The process of claim 1 wherein the amine is laury-lamine.

12. The process of claim 1 wherein the amine is 2-ethy-1- hexylamine.

13. The process of claim 1 wherein the amine is distearylamine.

14. The process of claim 1 wherein the amine is octadecyl-amine.

15. The process of claim 1 wherein the amine hydrohalide acceptor is a member selected from the group consisting of pyridine, 2,6-lutidine, collidine, trimethylamine, triet-hyl-amine, tripropylamine.

References Cited by the Examiner Goldberg: J. Chem. 500., pages 464-67 (1945). Petrov et al.: Zhur. Obsch. Khim., vol. 29 (May 1959), pages 1494-96.

JOHN D. RANDOLPH, Primary Examiner.

WALTER A. MODANCE, Examiner.

H. I. MOATZ, Assistant Examiner. 

1. A METHOD WHICH COMPRISES REACTING A B-HALO-ETHANESULFONYL HALIDE WITH ONE MOLAR EQUIVALENT OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYL AMINE HAVING FROM 1 TO 20 CARBON ATOMS, DI-ALKYL AMINE IN WHICH EACH ALKYL HAS FROM 2 TO 20 CARBON ATOMS, ALKENYL AMINE HAVING FROM 3 TO 20 CARBON ATOMS, DI-ALKENYL AMINE IN WHICH EACH ALKENYL HAS FROM 3 TO 20 CARBON ATOMS, AND BENZYLAMINE AT A TEMPERATURE IN THE RANGE OF 40* C. TO -80* C. AND IN THE PRESENCE OF AN AMINE HYDROHALIDE ACCEPTOR, AND RECOVERING THE RESULTING CORRESPONDING ETHYLENESULFONAMIDE. 